EP0440799A1 - Supraleitfähiges drahtmaterial und verfahren zur herstellung - Google Patents

Supraleitfähiges drahtmaterial und verfahren zur herstellung Download PDF

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Publication number
EP0440799A1
EP0440799A1 EP90907477A EP90907477A EP0440799A1 EP 0440799 A1 EP0440799 A1 EP 0440799A1 EP 90907477 A EP90907477 A EP 90907477A EP 90907477 A EP90907477 A EP 90907477A EP 0440799 A1 EP0440799 A1 EP 0440799A1
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EP
European Patent Office
Prior art keywords
superconducting
wire
substance
superconducting wire
filament
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90907477A
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English (en)
French (fr)
Other versions
EP0440799A4 (en
EP0440799B1 (de
Inventor
Ohsuke Miura
Kaname Matsumoto
Yasuzo Tanaka
Shoji Shiga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Furukawa Electric Co Ltd
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Furukawa Electric Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP1219385A external-priority patent/JPH0384813A/ja
Priority claimed from JP2001400A external-priority patent/JPH03205707A/ja
Priority claimed from JP2012886A external-priority patent/JPH03216915A/ja
Priority claimed from JP2060757A external-priority patent/JPH03263714A/ja
Application filed by Furukawa Electric Co Ltd filed Critical Furukawa Electric Co Ltd
Publication of EP0440799A1 publication Critical patent/EP0440799A1/de
Publication of EP0440799A4 publication Critical patent/EP0440799A4/en
Application granted granted Critical
Publication of EP0440799B1 publication Critical patent/EP0440799B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/20—Permanent superconducting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/01—Manufacture or treatment
    • H10N60/0184—Manufacture or treatment of devices comprising intermetallic compounds of type A-15, e.g. Nb3Sn

Definitions

  • Jc One method of increasing Jc is increasing the pinning force for capturing magnetic flux in a superconducting wire within a magnetic field produced by a coil of the superconducting wire, which magnetic flux enters the superconducting wire. This method is called “pin stop”, and a portion having the pin stop effect is termed “pinning center.”
  • an alloy superconducting wire is subjected to heat treatment at the time of final wire drawing, and a normal conducting deposited portion or strained portion, produced through the heat treatment, is employed as a pinning center.
  • a pinning center in a compound superconducting wire is normally present at a grain boundary.
  • the pinning center in the compound superconducting wire may be explained, for example, with reference to a manufacturing method illustrated in Figs. 5A to 5E.
  • An Nb or Nb alloy ingot 41 as shown in Fig. 5A, is buried in a bronze (containing Sn) pipe 42, as shown in Fig. 5B.
  • the resultant structure is processed into a hexagonal wire element 43 (see Fig. 5C).
  • a plurality of wire elements 43 are gathered and buried in a bronze (containing Sn) pipe 44.
  • the resultant structure is subjected to wire drawing, as illustrated in Fig. 5E, it is thermally treated to produce an intermetallic compound layer (Nb3Sn layer), thus obtaining a superconducting wire.
  • the intermetallic compound of the superconducting wire is a polycrystal.
  • a cross-sectional structure of the polycrystal is shown, for example, in Fig. 5F. That is, there are crystal grains 45 of Nb3Sn and grain boundaries 46.
  • these parameters are controlled by varying the temperature and time for heat treatment or adding a third substance, such as Ta, Ti, Hf or Ga in a Nb core or a matrix to make the grain boundaries dirty.
  • a pinning force Fp and an applied magnetic field B have the relationship: Fp ⁇ (1-B/Bc) 2 where Bc: critical magnetic field.
  • the present invention has been made in consideration of the above circumstances and its object is to provide a superconducting wire made of various superconducting substances and having enhanced pin stop effect and Jc, and to provide a method of manufacturing the superconducting wire.
  • the present invention provides a superconducting wire having a filament composed of a plurality of superconducting wire elements, characterized in that the filament contains a pinning center made of a non-superconducting substance.
  • the superconducting wire of this invention includes any one of an alloy-based superconducting wire, a compound-based (intermetallic compound) superconducting wire and an oxide-based high-temperature superconducting wire.
  • the pinning center is made of a wire of a non-superconducting wire buried in the superconducting wire element along the longitudinal axis of the filament.
  • the alloy-based superconducting wire can be manufactured by a method comprising the steps of: burying a wire of non-superconducting substance in the longitudinal direction of the superconducting wire; gathering a plurality of superconducting wire elements in which the non-superconducting wires were buried; drawing the gathered wire elements into a filament; and gathering a plurality of said filaments and reducing the diameter of the resultant structure.
  • the alloy-based superconducting wire can be manufactured by a method comprising the steps of: burying a plurality of wires of non-superconducting substance in the longitudinal direction of the superconducting wire; reducing the diameter of the resultant structure to obtain a filament; and gathering a plurality of the filaments and reducing the diameter of the resultant body.
  • the diameter of the wire of non-superconducting substance be 0.5 to 500 nm.
  • the diameter of the wire of non-superconducting substance is less than 0.5 nm, this diameter is too small as a pinning center, and it is difficult to pin-stop the lattice of magnetic flux.
  • the enhancement of Jc cannot be expected.
  • the diameter of the wire exceeds 500 nm, the matching with the lattice of magnetic flux is deteriorated and the enhancement of Jc cannot be expected.
  • this method it is possible to freely control, at the design stage, the size, type, shape, distance and position of the pinning center of non-superconducting substance introduced into the filament, in accordance with the use of the wire, e.g. the intensity of magnetic field.
  • the matching with the lattice of magnetic flux can be enhanced and the elemental pinning force can be effectively exhibited and increased, whereby Jc can be greatly improved.
  • the manufacturing time and cost can be reduced.
  • a shorter axis of the oval cross section of the wire of non-superconducting substance may be 100 nm or less.
  • the aspect ratio (length of a longer axis/length of a shorter axis) of the oval cross section of the pinning center be 2 or more. If the aspect ratio is less than 2, the surface pinning effect becomes undesirably low.
  • the alloy-based superconducting wire having the wire of non-superconducting substance with an oval cross section can be obtained by rolling the alloy-based superconducting wire manufactured by the above-stated method.
  • the non-superconducting substance for forming the pinning center be Cu or a Cu alloy; Cu or a Cu alloy coated with Nb or Ta; Cu or a Cu alloy mixed with 0.5 to 5 % by weight of magnetic substance; Cu or a Cu alloy coated with Nb or Ta and mixed with 0.1 to 5 % by weight of magnetic substance; a precious metal such as Ag or Au, or an alloy thereof; or a precious metal such as Ag or Au, or an alloy thereof, which is mixed with 0.5 to 5 % by weight of magnetic substance.
  • the filament may be a spiral element formed by alternately laminating a foil of superconducting substance and a foil of non-superconducting substance which becomes a pinning center.
  • the lamination cycle ⁇ of the foil of the superconducting substance and the foil of the non-superconducting substance be in the range of 5 nm ⁇ ⁇ ⁇ 100 nm, and the ratio of the area in the cross section of the filament, which area is occupied by the non-superconducting substance, be 40 % or less.
  • the ratio of the area exceeds 40 %, the non-superconducting substance serving as a pinning center becomes too large, and the non-superconducting substance is present at areas other than the area for trapping magnetic flux.
  • the Jc is deteriorated.
  • the lamination cycle ⁇ means the total thickness of the layer of superconducting substance and the layer of non-superconducting substance.
  • the alloy-based superconducting wire in which the filament is the spiral element can be manufactured by a method comprising the steps of: alternately laminating a foil of superconducting substance and a foil of non-superconducting substance to form a spiral element; and burying the spiral element in a normal conducting metal, and reducing the diameter of the resultant body.
  • a Jelly Roll method employed for manufacture of a compound superconducting wire is applied.
  • a thin foil is used as a starting material. Therefore, compared to a conventional multi-stack method, the distance between the superconducting substance and non-superconducting substance can easily been set at a nanometer order corresponding to the distance between magnetic fluxes, without applying a high draft. As a result, Jc can be greatly improved.
  • the superconducting wire of this invention may be a compound-based superconducting wire which can be manufactured, for example, by the following method.
  • rods of non-superconducting substance such as Ta, Cu, Ti, Al, Ge, Mg, Zn, Zr, Ni, Hf or Cr, are buried in a plurality of holes formed in a NbTi billet.
  • the outer peripheral surface of the NbTi billet is coated with a Cu sheath.
  • the resultant structure is hot-extruded and drawn, and the Cu sheath is removed, thereby obtaining a primary wire element.
  • a plurality of primary wire elements are inserted into a bronze billet (Sn content: e.g. 10 or more % by weight).
  • the resultant body is subjected to hot extrusion and then to process annealing and wire drawing which is repeated.
  • a secondary wire element is obtained.
  • the secondary wire element is subjected to the same treatment as the primary wire element, and is finally subjected to heat treatment, thus obtaining a compound-based (e.g. Nb3Sn) superconducting wire.
  • non-superconducting substance introduced into the filament, or superconducting substance having a difference in thermodynamic critical magnetic field (Hc) is extruded and drawn and made to function as a pinning center effectively.
  • the elemental pinning force can be increased, and Jc can be enhanced in a high magnetic field close to a critical magnetic field.
  • the grain boundary of crystal grains of superconducting substance or Nb3Sn functions as a pinning center, and also non-superconducting substance existing independently of the grain boundary functions as a pinning center.
  • the volume ratio of the non-superconducting substance, such as Ta, in the filament of the compound-based superconducting element be 50 % or less
  • This superconducting wire can be manufactured by a method comprising the steps of: gathering a plurality of core wires made of at least one selected among the group consisting of Nb, a Nb alloy, V, and a V alloy; burying the gathered core wires in a Sn-containing bronze pipe and, in this state, integrating the core wires by a composing process, and reducing the diameter of the resultant structure to obtain a composite wire; gathering a plurality of the composite wires, burying the composite wires in a Sn-containing bronze pipe, and drawing the resultant structure; and finally subjecting the drawn structure to heat treatment.
  • the composing process means a method of integrating a plurality of bundled core wires and reducing the diameter of the integrated body, for example, by hot extrusion or drawing, thereby obtaining a composite wire.
  • the core wire can be manufactured, for example, by inserting a Nb ingot into a Cu pipe, subjecting the resultant body to hot extrusion and drawing, and dissolving the Cu pipe away with use of nitric acid.
  • the core wire may be formed by coating a Nb wire, a Nb-alloy wire, a V wire or a V-alloy wire with one or more selected among the group consisting of Ta, Ti, Al, Ga, Mg, Zn, Zr, Hf, Cr and Fe.
  • the Sn-containing bronze pipe may have a composition of, for example, 14.3 % by weight of Sn, 0.2 % by weight of Ti, and Cu as the balance.
  • the superconducting wire of this invention is an oxide-based high-temperature superconducting wire
  • this wire can be composed of a plurality of filaments.
  • Each filament comprises a plurality of superconducting wire elements each having a pinning center formed by diffusing non-superconducting substance.
  • the oxide-based high-temperature superconducting substance is not limited, in particular.
  • Bi-Sr-Ca-Cu-O based substance, or Y-Ba-Cu-O based substance, or La-Sr-Cu-O based substance may be used.
  • non-superconducting substance a low-boiling-point substance such as K or FeCl3 may be used, taking into account the diffusion into superconducting substance.
  • the oxide-based high-temperature superconducting wire can be manufactured, for example, by the following method. Oxide powder produced by thermal decomposition or the like is filled in a metallic pipe. The resultant structure is cold-worked to a predetermined size by means of fluted roll or drawing. In this state, or, if necessary, with the metallic pipe removed, the resultant body is subjected to heat treatment in oxygen atmosphere. Thus, an oxide-based high-temperature superconducting wire is obtained. Thereafter, a coil made of this oxide-based high-temperature superconducting wire and non-superconducting substance are stored in sealed containers separately.
  • the oxide-based high-temperature superconducting wire and the non-superconducting substance are heated up to a predetermined temperature and vacuum-drawn into an oxide-based high-temperature superconducting wire in which the non-superconducting substance serving as pinning center is diffused.
  • This invention provides a superconducting wire having a filament composed of a plurality of superconducting wire elements, characterized in that the filament has an oval cross section.
  • a shorter axis of the oval cross section of the filament be 1 ⁇ m or less.
  • the aspect ratio (length of a longer axis/length of a shorter axis) of the cross section of the filament be 2 or more. If the aspect ratio is less than 2, the surface pinning effect is insufficient.
  • the filament has an oval cross section with a shorter axis being less 1 ⁇ m or less, and therefore the surface pinning effect can sufficiently be exhibited.
  • the volume of magnetic fluxes crossing the filament is increased and the pin stop effect is enhanced. According to this invention, it is not necessary to strictly determine the conditions for extrusion, working and heat treatment, and it is possible to reduce the number of heat treatment steps.
  • the outer periphery of a Cu rod having a diameter of 3 mm was coated with a Nb sheet.
  • the Cu rod was inserted into a through hole formed in a central part of a NbTi alloy wire having a diameter of 35 mm.
  • a plurality of NbTi alloy wires were inserted into a Cu billet having a diameter of 453 mm. Thereafter, the Cu billet was hot-excluded at 700 °C and drawn (the billet was removed during drawing), thus obtaining a superconducting wire element 1 of NbTi alloy having a hexagonal final cross section and a distance of 1.83 mm between parallel sides.
  • the Cu rod serves as a pinning center, as will be described below.
  • Fig. 1A 253 superconducting wire elements 1 were gathered and inserted into a Cu-10% Ni alloy billet 2 having its outer peripheral surface coated with Nb and having a diameter of 453 mm.
  • the resultant body was hot-extruded at °C and the diameter thereof was reduced, thus obtaining a secondary wire element (filament) 3 having a hexagonal final cross section and a distance of 3.15 mm between parallel sides (see Fig. 1B).
  • the secondary wire element 3 is a composite of a number of superconducting wire elements 1.
  • a tertiary wire element 5 having a hexagonal final cross section and a distance of 2.6 mm between parallel sides (see Fig. 1C).
  • the tertiary wire element 5 is a composite of a number of secondary wire elements 3.
  • the 241 tertiary wire elements 5 were gathered and buried in a CU billet 6 having a diameter of 453 mm, as shown in Fig. 1C.
  • the resultant structure was hot-extruded at 600 °C and the diameter thereof was reduced, thus obtaining a superconducting wire 7 having a diameter of 10 mm or less. If the cross section of each superconducting wire element 1 constituting the superconducting wire 7, it is found that a Cu pinning center 9 coated with a Nb sheet is present at the center of a hexagonal NbTi alloy 8 (see Fig. 1D).
  • the superconducting wire 7 had the diameter of 0.2 mm
  • the diameter of the filament 3 was 0.507 ⁇ m
  • the diameter of the pinning center 9 was 3.7 nm
  • the distance between adjacent pinning centers 9 was 30 nm.
  • any of the superconducting wires according to the present Example has a Jc remarkably higher than that of conventional superconducting wire No. 12.
  • the wires Nos. 2, 3, 7 and 8 have higher Jc than conventional wire No. 11.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
EP90907477A 1989-08-25 1990-05-28 Supraleitfähiges drahtmaterial und verfahren zur herstellung Expired - Lifetime EP0440799B1 (de)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP219385/89 1989-08-25
JP1219385A JPH0384813A (ja) 1989-08-25 1989-08-25 超電導線
JP1400/90 1990-01-08
JP2001400A JPH03205707A (ja) 1990-01-08 1990-01-08 化合物超電導線の製造方法
JP2012886A JPH03216915A (ja) 1990-01-23 1990-01-23 化合物超電導線材
JP12886/90 1990-01-23
JP2060757A JPH03263714A (ja) 1990-03-12 1990-03-12 超電導材料の製造方法
JP60757/90 1990-03-12
PCT/JP1990/000680 WO1991003060A1 (fr) 1989-08-25 1990-05-28 Materiau filaire supraconducteur et procede de production d'un tel materiau

Publications (3)

Publication Number Publication Date
EP0440799A1 true EP0440799A1 (de) 1991-08-14
EP0440799A4 EP0440799A4 (en) 1992-05-13
EP0440799B1 EP0440799B1 (de) 1995-10-11

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EP90907477A Expired - Lifetime EP0440799B1 (de) 1989-08-25 1990-05-28 Supraleitfähiges drahtmaterial und verfahren zur herstellung

Country Status (6)

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EP (1) EP0440799B1 (de)
KR (1) KR0158459B1 (de)
CA (1) CA2033325C (de)
DE (1) DE69022972T2 (de)
FI (1) FI103222B1 (de)
WO (1) WO1991003060A1 (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0487240A2 (de) * 1990-11-19 1992-05-27 General Electric Company Niob-Zinn-Supraleiter
DE4317703A1 (de) * 1992-06-19 1993-12-23 Furukawa Electric Co Ltd Supraleitender Draht aus einer Nb-Ti-Legierung und ein Verfahren zu dessen Herstellung
EP0600407A1 (de) * 1992-11-30 1994-06-08 Hitachi, Ltd. Nb3Al-Supraleiter, Herstellungsverfahren, Vorläufer-Zusammensetzung und supraleitender Magnet
EP1746667A1 (de) * 2005-07-19 2007-01-24 Bruker BioSpin AG Supraleitende Elemente mit Kupfer-Einschlüsse enthaltenden Nb3Sn-Filamenten, sowie ein Verbundwerkstoff und ein Verfahren für ihre Herstellung

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006032190A (ja) * 2004-07-20 2006-02-02 Mitsubishi Electric Corp Ｎｂ−Ｓｎ化合物系超電導線及びその前駆体
CN113122744A (zh) * 2021-04-19 2021-07-16 西安欧中材料科技有限公司 一种粉末冶金制备NbTi基超导材料的方法
CN114822981B (zh) * 2022-06-20 2022-09-20 西部超导材料科技股份有限公司 一种热挤压法制备铌三铝超导线材的方法
CN116580894B (zh) * 2023-07-13 2023-10-13 西安聚能超导线材科技有限公司 一种超细NbTi丝的制备方法

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US3465430A (en) * 1966-01-27 1969-09-09 Imp Metal Ind Kynoch Ltd Method of making superconductor stock
US4078299A (en) * 1972-09-11 1978-03-14 The Furukawa Electric Co. Ltd. Method of manufacturing flexible superconducting composite compound wires
GB2038532A (en) * 1978-11-24 1980-07-23 Atomic Energy Authority Uk Super-conducting members
US4803310A (en) * 1987-05-04 1989-02-07 Intermagnetics General Corporation Superconductors having controlled laminar pinning centers, and method of manufacturing same

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JPS51126789A (en) * 1975-04-28 1976-11-05 Agency Of Ind Science & Technol Ultra-fine multi-wick type super electroconductive lead-cable
US4414428A (en) * 1979-05-29 1983-11-08 Teledyne Industries, Inc. Expanded metal containing wires and filaments
JPS61174365A (ja) * 1985-01-29 1986-08-06 Sumitomo Electric Ind Ltd Ｎｂ３Ｓｎ化合物超電導線の製造方法
JPS61174366A (ja) * 1985-01-29 1986-08-06 Sumitomo Electric Ind Ltd Ｎｂ↓３Ｓｎ化合物超電導線の製造方法
JPH0680566B2 (ja) * 1985-04-09 1994-10-12 古河電気工業株式会社 Ｎｂ−Ｔｉ合金系超電導線
JPH0619930B2 (ja) * 1985-11-07 1994-03-16 工業技術院長 ニオブ・チタン極細多芯超電導線
JPH0642334B2 (ja) * 1985-11-08 1994-06-01 住友電気工業株式会社 複合多芯超電導線
JPH0791623B2 (ja) * 1986-03-11 1995-10-04 株式会社フジクラ Ｎｂ３Ｓｎ超電導線の製造方法
JPS62283505A (ja) * 1986-05-31 1987-12-09 住友電気工業株式会社 交流用超電導線
JPH02148517A (ja) * 1988-11-29 1990-06-07 Furukawa Electric Co Ltd:The 超伝導線材およびその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3465430A (en) * 1966-01-27 1969-09-09 Imp Metal Ind Kynoch Ltd Method of making superconductor stock
US4078299A (en) * 1972-09-11 1978-03-14 The Furukawa Electric Co. Ltd. Method of manufacturing flexible superconducting composite compound wires
GB2038532A (en) * 1978-11-24 1980-07-23 Atomic Energy Authority Uk Super-conducting members
US4803310A (en) * 1987-05-04 1989-02-07 Intermagnetics General Corporation Superconductors having controlled laminar pinning centers, and method of manufacturing same

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See also references of WO9103060A1 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0487240A2 (de) * 1990-11-19 1992-05-27 General Electric Company Niob-Zinn-Supraleiter
EP0487240A3 (en) * 1990-11-19 1992-08-26 General Electric Company Niobium-tin superconductor
DE4317703A1 (de) * 1992-06-19 1993-12-23 Furukawa Electric Co Ltd Supraleitender Draht aus einer Nb-Ti-Legierung und ein Verfahren zu dessen Herstellung
DE4317703C2 (de) * 1992-06-19 2002-12-05 Furukawa Electric Co Ltd Supraleitender Draht aus einer Nb-Ti-Legierung und ein Verfahren zu dessen Herstellung
EP0600407A1 (de) * 1992-11-30 1994-06-08 Hitachi, Ltd. Nb3Al-Supraleiter, Herstellungsverfahren, Vorläufer-Zusammensetzung und supraleitender Magnet
US5628835A (en) * 1992-11-30 1997-05-13 Hitachi, Ltd. Nb3 Al Group superconductor containing ultrafine Nb2 Al particles
EP1746667A1 (de) * 2005-07-19 2007-01-24 Bruker BioSpin AG Supraleitende Elemente mit Kupfer-Einschlüsse enthaltenden Nb3Sn-Filamenten, sowie ein Verbundwerkstoff und ein Verfahren für ihre Herstellung
US7887644B2 (en) 2005-07-19 2011-02-15 Bruker Biospin Ag Superconductive elements containing copper inclusions, and a composite and a method for their production

Also Published As

Publication number Publication date
CA2033325C (en) 1998-08-18
CA2033325A1 (en) 1991-02-26
DE69022972T2 (de) 1996-04-18
FI103222B (fi) 1999-05-14
EP0440799A4 (en) 1992-05-13
EP0440799B1 (de) 1995-10-11
DE69022972D1 (de) 1995-11-16
FI911966A0 (fi) 1991-04-23
KR0158459B1 (ko) 1998-12-15
FI103222B1 (fi) 1999-05-14
WO1991003060A1 (fr) 1991-03-07

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